Bridge structure for ph measurement device



E. D. COLEMAN BRIDGE STRUCTURE FOR pH MEASUREMENT DEVICE Oct. 19, 1948.

2 Sheets-Sheet 1 Original Filed Jan. 25, 1959 O 19, 1948 E. D. COLEMAN ,6

BRIDGE STRUCTURE FOR pH MEASUREMENT DEVICE Original Filed 'Jan. 25, 1939 2 Sheets-Sheet 2 a2 if??? w 53 I J; 72 8 33-- W. 65 El 103 6 :1: 76 95 g 73 8 74 a? I 0 1 z 10 a Y Patented Oct. 19, 1948 BRIDGE STRUCTURE FOR 1111 MEASURE- MENT DEVICE Edwin D. Coleman, Maywood, Ill.

Original application February 8, 1940, Serial No. 317,805, which is a division of application Serial No. 252,779, January 25, 1939.

Divided and this application July 5, 1943, Serial No. 493,559

4 Claims.

This invention relates to ion activity measurement and control devices, such, for example, as a hydrogen ion measurement device and parts thereof.

This is a division of my co-pending application Serial Number 317,805 filed February 8, 1940, which itself is a division of my application Serial Number 252,779 filed January 25, 1939, and now Patent Number 2,311,976.

An object of the invention is the provision of a generally improved device for electrically measuring ion activity which is reliable both for scientific and control purposes and has greater ruggedness, accuracy, and simplicity in operation than similar devices heretofore known, and the combination therewith of improved recording and control means.

An object of the invention is also to provide an ion activity measuring device having improved cell chain construction.

A further object is the provision of an ion activity measuring device having improvedmeans for bringing the test electrode and the solution into operative relationship.

Another aim of the invention is the provision of an electric ion activity measurement device having improved means for producing and for renewing the liquid junction thereof.

I have also aimed to provide an electric ion activity measuring device'having improved means for storing the junction material and improved means for dispensing the same.

A still further object of the invention is the provision of an electric ion activity measuring device having improved relationship betweenthe bridge material and the reference electrode. 7 1

A still further object is the provision of an ion activity measuring device having improved means for automatically and continuously or intermittently renewing the liquid'junction. j

A further object of the invention is the provision of an ion activity measurement device having an arrangement to accommodate improved bridge material.

A still further-object of'the invention is the provision of a bridge material of improved composition, such as to produce improved operating characteristics in a cell chain embodying the same and arranged to facilitate the renewal of the liquid junction either by manual or by automatic means during the operation of a, testing device.-

Other objects and advantageszwill appearfrom the following description and the accompanying drawings, in which Figure 1 is a horizontal section through the cabinets housing the electrodes, salt bridge, and a part of the temperature compensation mechanism: V

Fig. 2 is a vertical section through said cabinets;

Fig. 3 is a section on the line 33 of Fig. 2; and

Fig. 4 is a diagrammatic showing of means for automatically renewing the liquid junction.

I have herein shown and described the invention as embodied in a device for-the testing of solutions for pH, but it will be understood that many of the features thereof are not limited to the measurement of this particular property but may be applicable to the measurement and handling of other potentials of small magnitude and for analogous purposes.

Referring first to Figures 1 and 2, the cell chain includes a test electrode assembly designated generally by the numeral l2, a salt bridge 13, a reference electrode 14, and means for maintaining the salt bridge and renewing the liquid junction including the element 15 and the stop cock IS. The structure of the glass electrode assembly includes a glass electrode tube 11 and a tempera ture compensation tube l8 (Figs. 1 and 2). It will be understoodv by those skilled in the art that a metal electrode of suitable metal such as gold, platinum and antimony may be substituted for the glass electrode tube, in which instance the advantages of the mounting and sampling construction would still obtain. The glass electrode tube I! and temperature compensation tube iii are carried within a metal box designated generally by the numeral l9 'having a cover 2! secured across one face thereof by means of screws 22 which compress the cover againsta rubber or similar seal 23. Secured in the bottom wall of the box l9 are fittings 24, these fittings each having a hexagonal lower end and a cylindrical upper end 26 passing through openings in the box, the hexagonal lower end abutting'against the outer surface of the box so as to prevent passage of air therethrough. The cylindrical upper end 26 is threaded for the reception of a nut 21 for fixing the fitting in place, a lock washer 28 beinginterposed between the nut and the inner wall of the box, the whole forming a practically air-tight connection and providing electrical connection between the fittings and the box. The fittings have internal bores and internally threaded counterbores for the passage of liquid through the fitting and for the reception of inlet and outlet pipes 32 and 33. A further fitting designated generally by the numeral 34, which may be either of metal or of insulation material such as synthetic resin, is positioned against the top wall of results.

the box l9 and has a longitudinal bore extending from one end thereof to intersect a transverse bore connecting with the temperature compensation tube iii. A second transverse bore is provided adjacent the open end of the longitudinal bore, and the openrendsof the bores are normally closed by screw plugs as shown at '38 and ii threaded into the bores. The fitting 34 has nipples 44 which project through the top wall of the box I 9, insulation 46 and 41 being positioned :against opposite sides of the box when the fitting is of metal for the purpose of electrically insulating the fitting and the nipples from the box. The nuts 48 are threaded onto the nipples and serve to secure the fitting rigidly in position on :the box. The electrode tube I! is supported within the box between the nipple 44 and "the portion 26 of the fitting 25, the ends of the tube being in spaced relation to these elements and being secured thereon by flexible rubber sleeves 5| and 52.

Metal bands 53 and 54 clamp the rubber sleeves to the fittings, and clamps 55 and 56 likewise .clamp the.rubber sleeves to the ends of the electrode tube to provide fluid-tight connections of sufiici-ent flexibility so that the electrode tube cannotbe strained or will not be broken by sudden shocks either thermal or mechanical. The temperature tube IB is likewise connected, as shown in-my said prior patent.

Intermediate the ends of the electrode tube l1 and preferably at the mid-point therebetween is a junction tube 62 joining with the electrode tube through which the salt'bridge material is passed to establish the usual liquid junction with the contents of .the electrode tube, this junction being formed at the point indicated by the numeral 66. Equally'spaced from the point 63 areguard rings 64 and 65 on opposite sides of the point 53 and guard rings 66 and 6! equally spaced from the guard rings 64 and .65. Interposed between the guard rings 64 and 66 and the guard rings 65 and '6! and equally spaced therefrom .are contact .layers 68 and 69. I have found that intimate con- .tact between the surface of .the glass tube and the metal coating forming the guard rings and contact .layersis imperative for consistently good This contact maybe secured, 'for example, .by thermally dispersing ametal such as lead or silver over the glass surface preferably .by spraying thereon.

The solution under test is circulated through the interior of the electrode tube II, as for example, from a tank (not shown), the solution passing through the fitting .24, the electrode tube II, the nipp1e.M,.the fitting 34, the temperature the contact layers 68 and. 69 with respect to the liquid .junctionat '63 whereby .the effect of the I :transversecurrent on one of these contact layers is substantially compensated by the effect of the current on the other thereof .,In other words, if 'thedrop in potential between the liquid junction .63 and the electrode layer 68, is positive, the

.drop between the liquid junction 63,and the electrode layer569 will be negative and very nearly of thesame magnitude.

Liquid junction with the. sample within electrode tube 1.1 is established .at the point 63 by means of a column of conducting material, preferably a semi-plastic material such as agar gel.

In this instance, this column of conductive mate-' rial includes the tube 62 connected to a tube 12 by means of a rubber sleeve 13 which is in turn connected to a tube M by means of a rubber sleeve '55, the tube 14 extending through a rubber grommet 16 positioned in the back wall of the box I5 and in the side wall of a metal housing 17, the metal housing 11 being attached to the box-l fi'by-imeans of screws 18 and spacers i9.

'Theitube I4 is connected to the stop cock l6 by means of a, rubber sleeve 81 which is connected to the source of bridge material l5 and to the reference electrode 14 by means of tubes 82 and 83, :this system of tubes forming the conductive vcolumn or salt bridge [3. i3 is substantially filled with the bridge material The salt bridge tube bore 85 communicating with the interior of the tube-'86, and a threaded counterbore 86 threaded to receive an adapter 81 which is also provided with a'bore 88 adaptedto receive the threaded dispensing end 89 of a conventional collapsible tube 9]. The bridge material is carried in the tube 9| and is dispensedthrough the bore of the adapter 61 andthe bore of the fitting '84 into the tube '63. This arrangement is of considerable merit because of the diffiiculty of attaching the collapsible tube 9|. I have found that because of the nature of the threads on the dispensing end 8| 'of tubes o'f-thischaracter, which are commonly made of softmetal such as lead, extreme difficulty is encountered in threading the tube into position. I have therefore provided the adapter 81 which is screwed onto-the end of the tube prior to attachment into the vfitting 84 and the adaptor is subsequently screwed into the counterbore 86, thus permitting the adapter to be supplied to the tube in the openwhere greater care and accuracy can be obtained'in thefitting of the Darts.

'The bridge material is exposed to the sample in the electrode tube IT at the point 63, and as this surface continues to be so exposed, the concentration of KCl or other salt contained in the bridge material is gradually reduced until eventually appreciable error would be devoloped at 63 unless means were provided for replacing this surface witha fresh surface of bridge material su'ihciently rich in KCl. This is accomplished by opening the cocklfi and then compressing the tube 9!, thereby forcing bridge material from the tube into the salt bridge tube l3, discharging an equivalent amount of the exhausted bridge material at the point 63 from whence the exhausted material is rejected from the electrode tube with the flow of sample therethrough. The cock ]6 is closed during normal operation so that in the event of excessive fluid pressure in the electrodetube', this excessive pressure cannot be relieved "by driving th'ebridge material back into the collapsible tube 9] or into the reference electrode M.

The reference electrode is formed directly on the end 'of the tube 82 (see Fig. 3) and consists of an elongated glass bulb 92 having sealed in the bottom thereof a platinum or other suitable electrode 93 immersed-in mercury 94 covered in 4 turn with 'a layer 95 comprising a mixture of calomel and KCl. Positioned thereabove is a solution 96 consisting of saturated KC1 solution which fills the bulb and extends through the bore of the tube 82' to approximately the point 91 where contact is made with the bridge material. At the point where the bulb joins the tube 82 a small piece of glass wool 98 isfused into the wall of the electrode bulb to prevent the mercury from flowing into the tube 92, thus escaping from the bulb. The glass wool further functions to prevent granules of the bridge material from passing through the tube 82 and falling into the electrode proper. 'This assembly constitutes a novel type of saturated calomel half celLbut it will be understood that my invention is not limited to any particular form of half cell, but also contemplates in certain phases the use of half cells of other types, such as the unsaturated calomel half cell or other half cells well known in the art, or similar devices for producing substantially constant potential between a metallic conductor and a fluid. It will be seen that I have not only provided a novel form of reference electrode, but in addition, novel meansfor re-making the liquid junction, and this, in com bination with the use of a sealed reference electrode, constitutes a highly improved and simple procedure for replacing the liquid junction without danger of contaminating the reference electrode and with a minimum of difficulty, time and efiort. I have also provided novel means for storing a reserve supply of bridge material, and novel means for replacing the supply.

In order to effect compensation for variation in temperature of the reference electrode, the reference electrode'is surrounded with a resistance coil 99 (Fig.3) having leads I9I and I02, and over the entire assembly is mounteda protective sheath I93, the resistance coil 99 being temperature sensitive. A lead I94 connects to the platinum terminal 93 of the reference electrode and constitutes one terminal of the cell chain con sisting of the reference electrode and the glass electrode.

Disposed within the box 11 are portions of the temperature compensation device including 'a meter I22, batteries H2 and I53, a polarity reversing switch I 49, a switch I2I, and avoltage divider operated by a knob I56, these parts being assembled on a mounting plate III, asdescribed in my said patent. The electrode tube I1 and the temperature tube I8, together'with their directly associated parts, are assembled within the box I9.

It will be realized that the sample 'bein'g'circu- I lated through the electrode tube and temperature 'tube may be at temperatures substantially dif* ferent from room temperature, and since the temperature of the sample may vary to aiconsiderable extent, I have found it desirable to .thermally isolate the reference electrode from the region'in which the temperature of the sample may exert any material effect. This is accomplished by mounting the electrode tube and the temperature tube within the box I9 and by providing the cover 2| and the gasket 23 to substantially hermetically seal the box. Furthermore, space is provided within the box for the reception of an open container of a desiccant such as fused calcium chloride, hydrous calcium sulphide, sulphuric acid, or other desiccant to substantially .free the air within the chamber from moisture. Thisis of particular importance where cold solutions are being passed through the electrode tube since otherwise condensation of moisture occurs on the outside of the glass electrode that may seriously interfere with the operation of the instrument because of short circuits between the various parts thereof. Furthermore, the arrangement is such that all adjustments and the cleaning of the electrodes is pose sible without entering the box I9. The electrical conductors and the salt bridge are brought through the box through rubber grommets which serve to seal the openings thereabout and prevent infiltration of moisture. The housing 11 is provided with a door, as indicated at I59 (Fig. 1) provided with a gasket IISI and secured in place by a wing nut I62 which may be opened to allow immediate access to the interior thereof for making adjustments in the electrical circuit as heretofore indicated.

In order to conduct the current from the glass electrode tube to the measuringinstrument, wire loops I63 and I64 extend around and in intimate contact with the contact layers 68 and 69 and are engaged by a conductor I (Fig. 2). Wire loops I66, I61, I68 and I59 likewise engage the guard rings 64, 65, 66 and 61 and are interconnected by a conductorI1I. The conductors I65 and HI are connected to a metal rod I 12 and to a metal tube, respectively, insulated therefrom, the rod and tube being enclosed in an insulating sleeve I19 as more fully described in my said patent, which extends from the interior of the box I9 through the housing 11 as shown in Fig. 1, the opposite end of rod I12 being connected to a lead I13'from which circuit is completed to the measuring instrument through a cable I14,'the lead I13 having a shield I15, so designed that the potential of the shield I 15 is at the same potential as the lead I13 when the potentiometer of the measuring circuit balances that of the cell. The shield I 15 is connected to the opposite end of the tube and thus to conductor HI and to the guard rings, these elements forming part of the so-called McClure circuit described in my aforesaid patent. Ceramic insulators I83 and I84 are in contact only with the conductor I1I or with regions'at the same potential as the conductor I13 and the shield I15, and therefore, no leakage can occurfrom the ceramic insulators due to surface leakage when the cell changes potential balance because where exists no difference of potential between the conductor I1I or the lead I13 and the adjacent portions of the McClure circuit including the elements I82 and I16. 'It is thus'possible to connect the glass electrode to the measuring device through the shield I15 without in any way disturbing the potential of the glass electrode lead including the conductor I65, the rod I12 and the lead I13 by stray'electrical leakagaand it is further possible to extend the cable I14 for distances of several hundred feet, since a cable of this construction cannot leak to thesconductor I13 when used in the electric-a1 circuits herein described.

The purpose of the guard rings 69 to 61, inclusive, is to prevent electrical leakage along the surface of the glass tube. These four guard rings are connected together and to the McClure circuit,- and hence, since the potential of this. circuit is the same ,as thatof the contactlayers 68 and .69 of-the glasselectrode at the point of balance, there can occur noleakage from the contact layers along the surface.of theglass tube. I

In Fig. i I'have shown, means for automatically; replacing the liquid JllllCtiOlljat 63 (Fig. 2). This devicoincludes a cylinder52 4 having a threaded outlet end 525 somewhat similar in nature to the threaded outlet 89 of'tub'e 9| (Fig.3) adapted to be' threaded into thememben' 8:1 *irrzplace: ofi'the collapsible metal:tube-9l-:.o'f-:'Eig; 3 and'adapted to hold a supply of bridgelmaterial'indicated at 52$; A plunger 5211 is positionediin'theficylinder 52 and hasa threaded stem: 528 upn1W1'1ic11is positioned a worm wheel 529' securedla'gainst lateral movement and'irotatedi-bymeans: ofia. reduction gear train indicatedgenerally by theinumeral 53! and driven-by a motorrfi3'2'connected to a source of power'by lea'd's 533. Ifdesired; switch contacts may be interposed:- in this "power supply for the purpose of" intermittently aotuatingcthe motor and feeding the bridgematerialto the'liq uid junction in astep-by-stepfashion. Asishown, the mechanism continuously feeds bridge mate'- rial, the gear trainz53lbeing. suchastotvery slowly advance the plunger 521 and continuously'replace the bridge material:

While any suitableformofbridgematerialmay be employed, Ihave-found it particularly desirable to-employ a novel typeof bridge'materialzin the formof a plastic composition incapable of fiow-ing under its own hydrostatic pressure. A suitable material is formedb'y heating together one hundred grams of: water, two grams 'of agar over a steam bath until the mixture is clear. Thereupon aboutithirtygrams of potassium chloride is dissolved therein and the massa'llowed to cool and remainquiescent until a gel is Well established'. lfhe gel massisthen forced through a mesh screen torupture the gel and render the mass plastic; This latter step'breaksup the gel into small particles rendering the same sufficiently plastic: to flow "under moderate pressure. Ihave' found, however, that a preferred type of composition results from'the use in the combination of a plasticizersuch as glycerol, ethylene glycol, diethylene glycol, or sulfonated castor oil. This is'desirable'sinceit avoids the difiiculty here tofore associated with-the use. of bridge materials in their tendency toseep out anddry around the edges of a stop cook or at the'junctiorroftubes; When such a plasticizer is" used the gel remains permanently plastic" and" theabove mentioned difficulties' are not encountered; This preferred type of composition can be made as follows: About 30 grams of agar and'180"cc. ofwater are heated over a water bath until clear. About 2 grams or methyl celluloseis then added to the solution near its'boiling' point and allowed to cool with stirring until the cellulosepeptizesand the solution becomes smooth andfree-of lumps. About cc. of lycerine are then added'and the-mass re-heated, whereupon aboutGO'grams of potassium chloride and about 100 gramsof barium sulphate are added and the mass stirred until the chloride is dis; solved and the sulphate is 'well dispersed. Material isthen cooledand well stirred justbefore the setting temperature is reached; The material is then allowed to stand 'to'produce a gel and when gelled, is forced througha mesh screen having'a mesh size in accordance with the degree of plasticity required, approximately thirty mesh screen being satisfactory for use in the apparatus herein disclosed;

Where in the specificationand claims a plastic or a plastic mass is referred to, the terms are used .in their commonly accepted sense in the science of rheology,v and, refer to amass which acts :asa rigid body. whenilan increasingforce is applied thereto until the force increases to I a critical point atwhich the mass. yields and flows as a. fluid. That is, there mustbe an initial increment of pressure whichidoesnot cause flow as 8 distinguished from a fluid which yieldsiand flows under any applied stress and agel in which the force'causes elastic deformation only and'which does notflow.

While I have thus described and illustrated specific'embodiments of the invention itwill be understood that this is by way of illustration and not limitation.

1. In a device for measuring ion activity, an electrode comprising a tube having. a bore through-which the-sample is passedior test pur poses; a bridge tube connecting with said bore intermediate its ends, a supply of plastic bridge materialincapable offlow'through said bridge tube under its own hydrostatic pressure but capable of easyfi'ow" through said tube under'moderatepressure, and means for forcing bridge ma terialithrough said bridge tube to establish liquid junction with said sample at the junction of said tubes; 7

2. The combination in a cell chain having a test electrode and a sample, of a salt bridge, comprisingv a bridge tube communicating with said sample, a plastic bridge material filling said tube, incapable of flowing therethrough under its own hydrostatic pressure, means for holding a reserve supply of bridge material comprising a collapsi ble metal tube; and means for connecting said metal tubelto said bridge tube comprising a fitting' having threaded engagement with said metal tube and with said bridge tube.

3. In a device for measuring ion activity, an electrode comprising a tube having a bore for the continuous passage of a sample for test purposes, a bridge tube connecting with said electrode, a reserve supply of gelatinous bridge material'capable of flow through saidctube under moderate mechanically applied pressure, and means for holding said reserve supply and for forcingthe' bridge material through said bridge tube to establish liquid junction with said sample comprisingacollapsible metal tube filled with bridge material, and means connecting said collapsible metal tube to said bridge tube.

4. In' an electrolytic cell chain, the combination" of aztest electrode for holding a test sample, a half'cell having a single opening therein, a salt bridge comprising a tube connecting said opening to said electrode, a tube joining said bridge tube between the half cell and the electrode, and a supply of bridge material in said tubes, a reserve supply of bridge material connected to the last mentioned tube, said bridge material being in the form of a mechanically ruptured conductive gel medium of substantially uniform. viscosity, and means for mechanically forcing said bridge material from said reserve supply through said bridge tube in'successive'increments to renew the liquid junction.

EDWIN D. COLEMAN.

REFERENCES CITED' Thefollowing references are of record in the file'of thispatent:

UNITED STATES PATENTS Number Name Date 1,262,808 Keyt Apr. 16, 1918 1,727,094 Bayliss Sept. 3, 1929 2,046,101 York June 30, 1936 (Other references on following page) Number Number Name Date Rapids Nov. 24, 1936 Stoewener June 29, 1937 Crocker Sept. 6, 1938 Morgan et a1. June 6, 1939 George Aug. 8, 1939 Allison Dec. 19, 1939 Muller et a1. Apr. 21, 1942 FOREIGN PATENTS Country Date France May 22, 1934 

